Supported catalysts have been widely used in industries because of easy handling and robustness, however, their catalysis improvement appears incrementle. High performance catalysts are central for the development of new generation energy conversion and storage technologies.1,2 While industrial catalysts can be optimized empirically by tuning the elemental composition, changing the supports, or altering preparation conditions in order to achieve higher activity and selectivity, these conventional catalysts are typically not uniform in composition and/or surface structure at the nano- to micro-scale. In order to significantly improve our capability of designing better catalysts, new concepts for the rational design and assembly of metal-metal oxide interfaces are desired. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical for achieving better reaction activities and selectivities.